Search Results (1,907)

Currently, lepidolite is considered an important natural alternative for obtaining lithium, given the difficulty in processing other species containing this metal. However, its mechanical preparation and beneficiation present considerable challenges and play a critical role in its efficient separation by flotation. This study explores the effect of particle size and dodecylamine concentration during flotation in a laboratory Denver cell. The results indicate that particle size significantly affects the finding in which the optimum was −90 + 75 μm, with a separation efficiency of 94%, and with only 2.067 × 10⁻⁵ M of dodecylamine (DDA) (5 g/t) at pH 11.0. The hydrophobicity of lepidolite was generated by the effect of the chemisorption of the cationic collector and the FTIR results indicate detection of the characteristic bands of the adsorption of DDA to the surface of lepidolite. Full article

The Long Interspersed Element-1 (L1) retrotransposon is an ancient genetic parasite that comprises a significant part of the human genome. ORF2p is a multifunctional enzyme with endonuclease (EN) and reverse transcriptase (RT) activities that mediate target-primed reverse transcription of RNA into DNA. Structural studies of LINE-1 ORF2p consistently show a single Mg²⁺ cation in the reverse transcriptase active site, conflicting with the common DNA polymerase mechanism which involves two divalent cations. We explored a reaction pathway of the DNA elongation based on the recent high-resolution ternary complex structure of the ORF2p. The combined quantum and molecular mechanics approach at the QM (PBE0-D3/6-31G**)/MM (CHARMM) level is employed for biased umbrella sampling molecular dynamics simulations followed by umbrella integration utilized to obtain the free energy profile. The nucleotidyl transfer reaction proceeds in a single step with a free energy barrier of 15.1 ± 0.8 kcal/mol, and 7.8 ± 1.2 kcal/mol product stabilization relative to reagents. Concerted nucleophilic attack by DNA O3′ and proton transfer to Asp703 occur without a second catalytic metal ion. Estimated rate constant ∼60 s⁻¹ aligns with RT kinetics, while analysis of the Laplacian of the electron density along the cleaving P-O bond identifies a dissociative mechanism. Full article

For the first time, an alternative and sustainable approach is reported using phenyl-2-pyridyl ketoxime (PPKO) as a selective extracting agent for the recovery of Cu(II) from alkaline solutions in the presence of tartrate ions. The advantages relative to conventional processes carried out in acidic media are outlined. Through potentiometric and spectrophotometric analyses, the sequential formation of a 1:2 metal cation–ligand Cu(II)-(PPKO)₂ complex was identified as the predominant species in alkaline aqueous solutions. The high removal capacity of the extractant for Cu(II), as assessed from liquid–liquid extraction, and its efficient performance are comparable to widely used commercial extractants. Thermodynamic studies of the complexation between the copper(II) ion and PPKO demonstrated that the process exhibits an endothermic character. A progressive decrease in the performance of the extractant was observed after reuse without a regenerative treatment. This deterioration was partially reversed through a controlled reprotonation process using an acetate buffer solution. Overall, the results support the potential of PPKO as an effective and selective alternative ligand for hydrometallurgical applications in alkaline medium. Full article

Climate change is having a significant impact on vine physiology and grape composition, leading to notable alterations in wine quality, such as reduced acidity, increased ethanol content, and higher pH levels. These effects are particularly problematic in arid and semi-arid regions, such as Mediterranean areas, where high summer temperatures and low rainfall accelerate the degradation of organic acids in grapes. As a result, wines produced under these conditions often lack the acidity required to preserve their freshness and enological quality. This study evaluated the effect of must acidification using cation-exchange resins on the composition and quality of red wines made from the Monastrell variety, comparing them with wines acidified using tartaric acid to reach the same target pH. The results showed that treating a portion of the must (20% and 30%) with cation-exchange resins significantly reduced wine pH values and increased total acidity compared to the control wine. A similar result was observed in wines acidified with tartaric acid. However, as an additional effect, the treatment with resin more markedly reduced the concentration of pro-oxidant metal cations such as iron, copper, and manganese, contributing to lower values of volatile acidity and a greater stability against oxidation of phenolic compounds. Must acidification with both methods improved wine color quality by increasing color intensity and decreasing hue values. Although no significant differences were found in the total concentration of phenolic compounds, variations were detected in their compositional profile. Furthermore, the acidification also affected the concentration and composition of aromatic compounds in the final wine. Sensory analysis revealed that the treated wines—particularly those made with must acidified using cation-exchange resins—exhibited greater aromatic intensity, more pronounced fruity notes, and reduced astringency, resulting in a fresher mouthfeel. In conclusion, must treatment with cation-exchange resins appears to be a low-cost good alternative compared tartaric acid addition for reducing pH and increasing acidity in Monastrell red wines, thereby enhancing their quality in winegrowing regions with arid or semi-arid climates. Full article

A novel series of multifunctional tacrine–quinoline hybrids were designed, synthesized, and evaluated as potential anti-Alzheimer’s agents. These compounds incorporate tacrine for cholinesterase’s inhibition and 8-hydroxyquinoline for metal chelation. Piperazine was selected as a linker to provide conformational flexibility and to create favorable cation–π interactions with residues in the mid-gorge region of AChE, enhancing dual-site binding with AChE to inhibit Aβ aggregation. In vitro studies demonstrated submicromolar inhibitory activity toward both AChE and BuChE, particularly for compounds 16e (IC₅₀ = 0.10 μM for AChE, 0.043 μM for BuChE) and 16h (IC₅₀ = 0.21 μM for AChE, 0.10 μM for BuChE). These compounds also exhibited potent inhibition of self-induced Aβ_1–42 aggregation (16e: 80.5% ± 4.4%, 16h: 93.2% ± 3.9% at 20 μM). Kinetic analyses revealed mixed-type inhibition, suggesting dual binding to both CAS and PAS of AChE. UV–vis spectrometry confirmed the chelation of Cu²⁺ and Zn²⁺ ions by the 8-hydroxyquinoline moiety. These findings highlight the tacrine–quinoline scaffold as a promising platform for the discovery of a multitarget-directed anti-AD drug. Full article

In order to enhance the corrosion resistance of aluminum alloys, mussel adhesive protein (MAP) was intercalated into layered double hydroxide (LDH) grown onto an Al substrate. The results from X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and energy dispersive spectroscopy (EDS) measurements all confirmed that part of the positively charged MAP can be successfully intercalated into the LDH based on the strong second reactivity. MAP is able to form complexes with the metal cations and hydroxides, leading to less positive charges on the hydroxide layers of the LDH. The intercalation results in the removal of the previously intercalated anions from the interlayer space of the LDH, which maintains the charge balance and lamellar structure. The MAP intercalated LDH film can provide effective corrosion protection to the Al substrate. Full article

Samples of gel-type cation exchangers of the TOKEM nomenclature were tested for lithium extraction from multicomponent natural brines. The dependencies of the extraction of Li and other impurities—Na, Ca, and Mg—on the duration of the sorption process for the tested ion-exchange resins under static conditions are presented. Metal ions can be arranged according to the degree of extraction for each ion exchanger in a row: Ca²⁺ < Mg²⁺ < Li⁺, Na⁺. Testing of ion exchangers under static conditions on technological Li-containing solutions confirms the applicability of TOKEM-140 and TOKEM-160 cation exchangers for lithium extraction. For TOKEM-140, lithium extraction over time varies from 76.2% to 73.8% and for TOKEM-160—from 73.8% to 72.4%. The ionic background of natural brines has a significant effect on the capacity of ion exchangers for lithium and forms the following series Li⁺ << Mg²⁺ < Ca²⁺ << Na⁺ relative to the obtained concentrations of metal ions in natural brine. The overlay of IR spectra of TOKEM-140 and TOKEM-160 ion exchangers before and after saturation shows slight changes in their appearance, indicating that the lithium sorption process has occurred. The values of static exchange capacity (SEC) for TOKEM-140 and TOKEM-160 cation exchangers are identical. Full article

The rational design of functional and sustainable polymers is central to addressing global environmental challenges. In this context, unmodified lignin derived from Sarkanda grass (Tripidium bengalense), an abundant agro-industrial lignocellulosic byproduct, was systematically investigated as a natural polymeric adsorbent for the remediation of aqueous media contaminated with heavy metals. The study evaluates lignin’s behavior toward nine metal(loid) ions: arsenic, cadmium, chromium, cobalt, copper, iron, nickel, lead, and zinc. Adsorption performance was systematically investigated under static batch conditions, optimizing key parameters, with equilibrium and kinetic data modeled using established isotherms and rate equations. Surface characterization and seed germination bioassays provided supporting evidence. Unmodified Sarkanda grass lignin demonstrated effective adsorption, exhibiting a clear preference for Cu(II) followed by other divalent cations, with lower capacities for As(III) and Cr(VI). Adsorption kinetics consistently followed a pseudo-second-order model, indicating chemisorption as the dominant mechanism. Thermodynamic studies revealed spontaneous and endothermic processes. Bioassays confirmed significant reduction in aqueous toxicity and strong metal sequestration. This work positions unmodified Sarkanda grass lignin as a bio-based, low-cost polymer platform for emerging water treatment technologies, contributing to circular bioeconomy goals and highlighting the potential of natural polymers in sustainable materials design. Full article

Natural zeolites have gained attention as low-cost adsorbents for the removal of heavy metals (HMs) from wastewater. However, their performance can be compromised by the presence of competing cations such as ammonium (NH₄⁺). This study investigated the competitive adsorption and desorption dynamics of NH₄⁺ and six HMs (Cd, Cr, Cu, Ni, Pb, and Zn) on two natural zeolites. Batch and column experiments using synthetic wastewater were conducted to evaluate the effects of different NH₄⁺ concentrations, pH, and particle size on HM removal efficiency and desorption effects. Results showed that increasing NH₄⁺ concentrations significantly reduce HM adsorption, with total capacity decreasing by ~45% at 100 mg/L NH₄-N in kinetic tests. Adsorption isotherms of the HM mixture for both zeolite types followed a clear sigmoidal trend, which was captured well by the Hill model (R² = 0.99), with loading rates up to 56.14 mg/g. Pb consistently exhibited the highest affinity for zeolites, while Cd, Cr, Ni, and Zn were most affected by NH₄⁺ competition in the column tests. Desorption tests confirmed that NH₄⁺ rapidly re-mobilises adsorbed metals, in particular Cd, Cu, and Zn. Slightly acidic to neutral pH conditions were optimal for minimising HM remobilisation. These findings underscore the need to consider competitive interactions and operational conditions when applying natural zeolites for HM removal, especially in ammonium-rich environments such constructed wetlands, soil filters, or other decentralised applications. Full article

The state of the art in the thermodynamics of calix[4]resorcinarene derivatives and its metal ion complexes is briefly discussed in the introduction. This is followed by the synthesis and characterization of a recyclable calix[4]resorcinarene amide derivative (L). The 1H NMR analyses in CD3CN and CD3OD showed solvent-dependent conformational changes with a notable downfield chemical shift in the aromatic proton (H-2) in moving from deuterated methanol to acetonitrile, indicating an interaction of the solvent within the ligand cavity as suggested by molecular dynamic simulations. 1H NMR complexation in acetonitrile revealed that L forms relatively strong 1:1 complexes with cations, with selectivity for Ca(II) and, to lesser extent, with Pb(II) over other metal cations. The composition of the complexes is corroborated by conductance measurements. The thermodynamics of these systems indicate that the complexation process is predominantly enthalpy controlled in acetonitrile, while it is entropy controlled in methanol. A remarkable outcome of fundamental studies is found in its application as new material for the removal of Ca(II) from water. The capacity of L to remove Ca(II) from water is 24 mmol/g which exceeds by far the capacity of cation exchange resins. Full article

Conductive hydrogels hold great promise for biomedical and electronic applications. However, their practical use is often limited by poor self-healing capability, which can affect long-term stability and durability. To address this, we developed alginate/polyacrylamide-based conductive hydrogels incorporating FeCl₃ and AlCl₃, named CH-Fe and CH-Al, respectively. We systematically studied the influence of metal cations on the hydrogels’ mechanical and electrical properties. CH-Al showed the most optimized performance, with a 329% increase in tensile strength and a 323% improvement in conductivity compared to the blank hydrogel. Additionally, CH-Al demonstrated excellent self-healing ability, with nearly 100% recovery after damage. The introduction of Al³⁺ improved conductivity by forming dynamic electron-conductive pathways through interactions with the polymer network. The self-healing behavior arises from reversible metal–ligand coordination bonds, which enable rapid recovery of the hydrogel’s structure after mechanical disruption. This study successfully developed a conductive hydrogel that combines high electrical conductivity, robust mechanical strength, and an intrinsic self-healing ability, offering significant potential for applications in bioelectronic devices, flexible sensors, and implantable medical technologies. Full article

Pyridyl-thiourea complexes of formula [(Cym)MCl(κ²N_py,S-H₂NNS)][SbF₆] (Cym = η⁶-p-MeC₆H₄iPr; H₂NNS = N-(p-tolyl)-N′-(2-pyridylmethyl)thiourea); M = Ru (1), Os (2)) were synthesized by reacting the corresponding metal dimers [{(Cym)MCl}₂(μ-Cl)₂] with H₂NNS in the presence of NaSbF₆. Subsequent chloride abstraction with AgSbF₆, followed by NH deprotonation using NaHCO₃, afforded the cationic complexes [(Cym)M(κ³N_py,N_amide,S-HNNS)][SbF₆] (M = Ru (5a), (5c); M = Os (6a, 6c)) and [(Cym)M(κ²N_amide,S-HNNS)][SbF₆] (M = Ru (5b); M = Os (6b)). The proposed structures for the prepared compounds are based on NMR data. Complexes 5a, 5b, and 6a, 6b evolve to the thermodynamically more stable species 5c and 6c, respectively, in which the deprotonated ligand HNNS adopts a κ³N_py,N_amide,S coordination mode. Complexes 5c and 6c activate H₂, behaving as frustrated Lewis pair (FLP) species, and catalyze (5c and/or 6c) the hydrogenation of polar multiple bonds, including the C=N bonds of N-benzylideneaniline and quinoline, the C=C bond of methyl acrylate, and the C=O bond of 2,2,2-trifluoroacetophenone. Full article

Selenium (Se) is a natural detoxifier of the heavy metal mercury (Hg), and the interaction between Se and Hg has been widely investigated. However, the ecological response of Hg to Se in Hg-contaminated farmland requires further study, especially the relationship between Se–Hg interactions and soil abiotic and biological properties. Through a field experiment, the effects of different levels of exogenous Se (0, 0.50, 0.75, 1.00, and 2.00 mg kg⁻¹) on Hg and Se transport in maize, soil properties, enzyme activities, and the microbial community in Hg-contaminated farmland were systematically studied. The Se treatments significantly reduced the Hg concentration in maize roots, stems, leaves, and grains and significantly increased the Se concentration in maize tissues. Except for the 0.75 mg kg⁻¹ Se treatment which significantly increased electrical conductivity compared to the control, other Se treatments had non-significant effect on soil physicochemical properties (pH, conductivity, organic matter content, and cation exchange capacity) and oxidoreductase activities (catalase, peroxidase, and ascorbate peroxide). The activities of soil invertase, urease, and alkaline phosphatase increased significantly after Se application, and the highest enzyme activities were observed with a 0.50 mg kg⁻¹ Se treatment. The bacteria and fungi with the highest relative abundance in this study were Proteobacteria (>30.5%) and Ascomycota (>73.4%). The results of a redundancy analysis and predictions of the microbial community showed that there was a significant correlation between the soil nutrient cycle enzyme activity, microbial community composition, and microbial community function. Overall, exogenous Se application was found to be a viable strategy for mitigating the impact of Hg stress on ecosystems. Furthermore, the results provide new insights into the potential for the large-scale application of Se in the remediation of Hg-contaminated farmland. Full article

The growing demand for ultra-low sulfur fuels has intensified interest in recovering strategic metals from the large volumes of hazardous hydrodesulfurization catalysts that are discarded yearly. This work evaluates a task-specific ionic liquid, tri-n-octylammonium bis(2-,4-,4-trimethylpentyl)-phosphinate [TOA][Cy272], synthesized by the acid–base neutralization of tri-n-octylamine and Cyanex 272. FT-IR spectroscopy confirmed complete proton transfer and the formation of a stable ion pair. Liquid–liquid extraction tests were conducted with synthetic Co–Ni–Mo solutions (0.1–2.5 g/L each), a varying ionic liquid concentration (10–50 vol%), pH (1.5–12.5), and organic/aqueous ratio (1:1). At 35 vol% of ionic liquid and pH 2, the extraction efficiency for Mo reached 94%, with separation factors βMo/Ni = 12 and βMo/Co = 7.5; Co and Ni uptake remained ≤15%. Selectivity decreased at higher metal loadings because of ionic liquid saturation, and an excessive ionic liquid amount (>35%) offered no benefit, owing to viscosity-limited mass transfer. Stripping studies showed that 1 M NH₄OH stripped about 95% Mo, while leaving Co and Ni in the organic phase; conversely, 2 M HCl removed 92–98% of Co and Ni, but <5% Mo. Overall Mo recovery of about 95% was obtained by a two-step extraction/stripping scheme. The results demonstrate that [TOA][Cy272] combines the cation exchange capability of quaternary ammonium ILs with the strong chelating affinity of organophosphinic acids, delivering rapid, selective, and regenerable separation of Mo from mixed-metal leachates and wastewater streams. Full article

The information on the seasonal variability of the chemical composition of the Arctic rivers is necessary for the proper assessment of the status of river runoff and the influence of anthropogenic and natural factors. Spring freshet is an especially important period for the Arctic rivers with a sharp maximum of water discharge. The Kolyma River is the least studied large river with a basin located solely in the permafrost zone. The change in the concentration of dissolved organic carbon (DOC), major, trace, and rare earth (RE) elements was studied at the peak and waning of the spring freshet of 2024 in the lower reaches of the Kolyma River. The concentration of elements was determined in filtrates <0.45 μm and in suspended solids > 0.45 μm. The content of coarse colloids (0.05–0.45 μm) was estimated by the intensity of dynamic light scattering (DLS). It was shown that the freshet peak is characterized by a minimal specific conductivity, concentration of major cations, and chemical elements migrating mainly in solution (Li, Sr, and Ba). During the freshet decline, the concentration of these elements increases with dynamics depending on the water exchange. The waters from the Kolyma River main stream have a maximal content of coarse colloids and concentration of <0.45 μm forms of hydrolysates (Al, Ti, Fe, Mn, REEs, Zr, Y, Sc, and Th), DOC, P, and heavy metals (Cu, Ni, Cd, and Co) at the freshet peak. A decrease of 8–10 times for hydrolysates and coarse colloids (0.05–0.45 μm) and of 3–6 times for heavy metals was observed at the freshet waning during the first half of June. This indicates a large-scale accumulation of easy soluble forms of hydrolysates, DOC, and heavy metals in the seasonal thawing topsoil layer on the catchment upstream in the previous summer, with a flush out of these elements at the freshet peak of the current year. In the large floodplain watercourse Panteleikha River, the change in concentration of major cations and REEs, Zr, Y, Sc, and Th at the freshet is less accented compared with the Kolyma River main stream due to a slower water exchange. Yet, <0.45 μm forms of Fe, Mn, Co, As, V, and P show an increase of 4–6 times in the Panteleikha River in the second half of June compared with the freshet peak, which indicates an additional input of these elements from the thawing floodplain landscapes and bottom sediments of floodplain watercourses. The concentration of the majority of chemical elements in suspended matter (>0.45 μm) of the Kolyma River is rather stable during the high-water period. The relative stability in the chemical composition of the suspended solids means that the content of the suspension and not its composition is the key to the share of dissolved and suspended forms of chemical elements in the Kolyma River runoff. Full article